Synthesis of (Z)‐1‐Aza‐1,3‐enynes by the Cross‐Coupling of Terminal Alkynes with Isocyanides Catalyzed by Rare‐Earth Metal Complexes

Abstract

Rare reactivity: A binuclear catalyst intermediate leads to the Z‐selective cross‐coupling of terminal alkynes with isocyanides to exclusively yield the (Z)‐1‐aza‐1,3‐enyne products for the first time (see scheme).

Methylidene Rare‐Earth‐Metal Complex Mediated Transformations of CN, NN and NH Bonds: New Routes to Imido Rare‐Earth‐Metal Clusters

“…Compound 10 a represents the first example of rare‐earth metal clusters with a μ 3 ‐η 1 ‐alkynide bridge 13. 14 The average YC (μ 3 ‐alkynide) bond length (2.464 Å) is slightly shorter than that of μ‐alkynide complex [{{Me 4 C 5 Si(Me 2 )NPh}Y(μ‐CCPh)} 2 ] 14. The average LuS bond length is 2.794 Å, which is shorter than that of complex [{(C 5 Me 5 ) 2 Y(μ‐SPh)} 2 ], but comparable to that of complex [(C 5 H 4 SiMe 2 t Bu) 2 Er(SBT)(thf)] (SBT=benzothiazole‐2‐thiolate), taking account of the difference between metal radii (Table 2).…”

Benzyllanthanide Chemistry: Revival of Manzer’s ortho‐Me2N‐Benzyl Ligand

“…This series of catalysts was tested in the addition of the phosphine P-H bond to carbodiimides and allowed screening of the metal size: an increase in the size of the metal results in increased activity. The same type of catalysts has shown good activity in the cross-coupling of various alkynes with isocyanide and shows an unprecedented Z-selectivity [29]. Catalysts of type 5, which contain the DMA ligand as the active part, showed the same activity as similar catalysts with CH 2 SiMe 3 as the active group.…”

Transition Metal and Inner Transition Metal Catalyzed Amide Derivatives Formation through Isocyanide Chemistry

“…115 Scheme 52 Pd-catalyzed cross-coupling reaction of 1,1-dibromoalk-1enes with isocyanides Catalytic monoinsertion of isocyanides into terminal alkynes for the construction of 1-aza-1,3-enynes using organoactinide and rare-earth metal complex, 116 Sm complex, 117 and half-sandwich rare-earth metal complexes has been reported. 118 Inspired by these reactions, in 2018 Wang, Ji, and co-workers developed an innovative threecomponent reaction of isocyanides, terminal alkynes, and water catalyzed by the Co(II)/Ag(I) system for the synthesis of alkynamides 172 (Scheme 53). 119 Co(II)/Ag(I) synergistically catalyzes the insertion of monoisocyanide into the C-H bond of the terminal alkyne, followed by oxidation and replacement of water to afford alkynamides 172.…”